Polyamides from 13 14 - diazatricyclo(6.4.1.12 7)tetradecane and 13 14 - diazatricyclo(6.4.1.12 7)tealexander l. johnson

ABSTRACT

FILMS AND FIBER FORMING POLYAMIDES FORM 13, 14-DIAZATRICYCLO(6,4.1.1**2,7) TETRADECANE AND 13,14 - DIAZATRICYCLO(6,4.1.1**2,7) TETRADECA-3,5,11-TETRANE.

Unitcdstates Patent O M U.S. Cl. 260-78 R 6 Claims ABSTRACT OF THE DISCLOSURE Film and fiber forming polyamides from 13,14-diazatricyclo[6.4.1.1 ]tetradecane and 13,14 diazatricyclo- [6.4.1.l ]tetradeca-3,5,9,1l-tetraene.

RELATED APPLICATION This application is a division of my copending application Ser. No. 529,961 filed Feb. 25, 1966 now U.S. Pat. 3,475,433.

BACKGROUND OF THE INVENTION Field of the invention I This invention relates to, and has as its principal objects provision of, polyamides, polyurethanes and polyamines from 13,14 diazatricyclo[6.4.1.1. ]tetradecane and 13,14 diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,11- tetraene.

Prior art In the Marsh U.S. Pat. 3,268,512 of Aug. 23, 1966, there are described and claimed dimeric azepines of the general formula wherein X represents certain substituents and m is a cardinal number in the range 0-6, inclusive, denoting the number of valences on the depicted carbons filled by substituents X. a

In my copending application Ser. No. 529,961 of which this application is a division, it is disclosed that the N-cyanozepine dimer of the foregoing general formula,

where mt=0, rearranges to a more stable and novel diazotricyclotetradecatetraene. The rearranged compound is partially hydrolyzed to the unsaturated diamine of the formula below 3,635,912 Patented Jan. 18, 1972 13,14-diazatricyclo 6.4JL1 tetradeca-3,5,9,11-ttetraene This compound in turn is hydrogenated to the saturated diamine of the formula 13,14-.diaaatricyclo 6.4.1.1 tetradecane Both the unsaturated and saturated diamine formthe usual hydrohalide salts such as the hydrochloride or hydrobromide which can be isolated from aqueous solution.

DESCRIPTION OF THE INVENTION The present invention comprises the preparation of useful polymers from the aforesaid unsaturated diamine and saturated diamine by reacting them with appropriate reactants.

EMBODIMENTS OF THE INVENTION There follow some nonlimiting examples illustrating the invention in more detail. All temperature values given are in degrees centigrade.

It may be noted that Formula I can be written to show the trans and cis stereoisomeric forms titans 8 Formula H can similarly be written to show the trans and cis stereoisomers of the saturated diamine and differs from the above of course in having the double bonds removed.

EXAMPLE 1 Preparation of a polyamide from 13,14 diazatricyclo- [6.4.1.1 ]tetradeca 3,5,9,11 tetraene and adipic acid Romans), co COCl l CO(CH )4 COzH i13,14 diazatricyclo[6.4.1.1 tetradeca 3,5,9,11 tetraene (0.27 g.) was suspended in a mixture of dichloromethane (10 ml.), water (40 ml.) and sodium hydroxide (0.12 g.) in a 300-ml. tall-form 'beaker. This mixture was agitated with a high-speed stirrer and treated at once with adipoyl chloride (0.25 g.). After 10 minutes stirring, the liquid was boiled for 5 minutes to remove dichloromethane, and then it was cooled to and filtered to remove the white polymeric suspension. The residue was The method of Example 1 was essentially employed to make additional polymers from 1 g. of 13,14-diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,l1 tetraene and 1 g. of various diacid chlorides [A(COCl) Data for these preparations are given in the following table:

Polymer Anal, percent Inli. vise. I.R.,em. NMR,T (CFQCOZH, Example A(COC1)2 C. C H N (KBr, vmax.) (CFaCOzH) 0.25%, 26 0.)

i329 5 4.8 2 Adlpoyl chloride 248 zg'g g? 1,645 5.52 7.81 8. 70 3, 02% 4.3g 1, 7 4. 7 a Suberoylchlorlde 230 1 650 5.46 7. 73 8.93 8, 4. 28 4. 74 4 Sebacoyl chloride 148-150 5.45 7. 71 "5&5; 8.99 4. 41 5 Ethylene glycol bischloroformate 100-105 g'gg 1, 710 5,37 5. 93

Norm-The polymers of Examples 1, 2, 3, and 4 are polyarnldes.

That of Example 5 is a polyurethane.

The polymers of Examples 2, 3 and 4 were pressed into films at a pressure of 500 p.s.i. and temperatures near their melting points. The films were self-supporting, those from 2 and 4 being somewhat brittle and that from 3 being flexible. A film from 3 (0.0036" thick) showed the following properties:

Refractive index: 1.57 Resistivity: ohm cm. Tensile strength:

7360 1b., 4.4% elongation at break 5240 lb., 3.0% elongation at break 7160 lb., 4.5% elongation at break Stiffness:

172,000 p.s.i.

160 000 p.s.i. 4.03 8 vinyl protons 45 t 5.50 exchange signal HDO EXAMPLE 6 7.58 4 CH protons adjacent to @0 Preparation of a polyamide from 13,14-diazatricyclo 8.33 4 CH protons remote from C=O [6.4.1.1 ]tetradecane and adipic acid (3001 .2HC1 11(0112 4uNaOH C001 NII C O(CHz)4'-CO2H 4% 1.

13,14 diazatricyclo[6.4.2.l 'qtetradecane hydrochloride (0.53 g.) was suspended in a mixture of dichloromethane (10 ml.) and Water (40 ml.), stirred rapidly, and treated in succession with sodium hydroxide (0.32

mina), cooled to and the combined ingredients stirred for minutes. One liter of n-hexane was added to precipitate the product, which was collected, washed with water, and dried at 100/ 1 mm. to give poly(13,14-diazag.) and adipoyl chloride (0.36 g.). The white powdery 5 tricyclo[6.4.1.1 ]tetradecane terephthalamide), 6.6 g., polymer was isolated as described in Example 1 (80 mg.), m (m-cresol)=0.66, polymer melt temperature 360. M.P. 315 (dec.). The product has the repeating structural unit shown above.

Analysis.-Calcd. for (C H N O (percent): C, EXAMPLE 12 71.01; H, 9.27; N, 9.20. Found (percent): C, 66.33, Pol (131453" 1 64112-7 tt d 66.34; H, 8.73, 8.79; N, 9.43, 928. 10 Y 1 isophthalamide) IRWEE; 3450 cm.- (in) (NH, CO H) 2940, 2860 cm. (w) (CH) 7 1740 cmr (vw) c0 11 0 1640 6111. (vs) (NCOR) l The method of Example 6 was employed to make addi- 15 0 tional polymers from 1 g. of 13,l4-diazatricyclo[6.4.1.1 ll tetradecane and 1 g. of various diacid chlorides O N A COCl )2]. i I Data for these preparations are g1ven 1n the following table: n

Polymer AnaL, percent Inh. vise. .P., I.R.,em. NMR,T (CF COzH, Example 0001). 0. C H N (KBr,vmax.) (CFaCOgH) 0.25%,25 0.)

i218 7 Adipeyl 611161166 3 5 gig 3. 11430 gIggI IIIIIIIIIII 8'. 77 I 2,910 5.41 8-... y 184-185 7812; 318i 3: il 7 :23 I "jiri' 3513 0 Sebacoylchloride -H5236 3133 5133i 11363 91231133133111: 8.87 5&1 m 824 2,940 6.54. 0.09 10 Eth 1 1 lbi 111 r t 105-110 1,695 5.76 Y W0 5 0 0m Orma e 58.06 7.41 s 21 11430 5O N orE.-The polymers of Examples 6, 7, 8, and 9 are polyamides. That The polymers of Examples 7, 8, 9 and 10 were pressed into films at a pressure of 500 p.s.i. and temperatures near their melting points. The films were all self-supporting though somewhat brittle. A film from Example 8 (0.0036 thick) showed the following properties:

Poly(13,14-diazatricyclo[6.4.1.l qtetradecane terephthalamide it it- 13,14-diazatricyclo[6.4.1.1 ]tetradecane (4.27 g., vacuum sublirned in chloroform (125 ml., chromatographed) and sodium hydroxide (1.8 g.) in 150 ml. of water (cooled to 0), were mixed in a high speed stirrer. To these stirred ingredients was added rapidly terephthaloyl chloride (4.46 g., vacuum distilled and vacuum sublimed) in chloroform (2-5 ml., chromatographed on acid-washed alu- Example 10 is a polyurethane.

The procedure of Example 11 was repeated, employing isophthaloyl chloride in place of the terephthaloyl chloride. The product was 7.12 g. of poly(13,14-diazatricyclo [6.4.1.1 ]tetradecane isophthalamide) having an inherent viscosity of 1.10 in m-cresol. It was readily pressed into a tough, self-supporting film under heat and pressure and has the repeating structural unit shown above.

EXAMPLE l3 Polyamine from 13,14-diazatricyclo[6.4.1.1 ]tetradecatetraene and p-xylylene dibromide A mixture of 1.0 g. of 13,14-diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,1l-tetraene, 1.50 g. of p-xylylene dibromide, 0.60 g. of anhydrous sodium carbonate and 50 ml. of absolute ethanol was heated at reflux for 20 hours and then evaporated to dryness. The residue was stirred with water and adjusted to pH 11 by addition of 25% aqueous sodium hydroxide. The pinkish residue was collected by filtration, washed with water and air dried to obtain 2.10 g. of a solid polyamine having the repeating structural unit shown above. The product melted above 375 and had an inherent viscosity of 0.25 in CF CO H at 25.

When the tetraene used in Example 13 is replaced by the corresponding tetradecane, Formula II, the polymer obtained has the structure wherein D is a divalent organic radical selected from the wherein R is alkylene of 3 to 14 carbon atoms or arylene of 6 to 14 carbon atoms; X is alkylene or oxygen-interrupted alkylene of 2 to 14 carbon atoms; and Y is alkylene of 1 to 14 carbon atoms or arylene of 6 to 14 carbon atoms. The divalent radicals R, X and Y are composed primarily of carbon and hydrogen and merely serve as inert carrier for the two reactive end groups on the difunctional acids, acid halides or dihalides used in the polymer-forming reaction with the diamines. Thus the polymers of the invention are derived by reaction of the corresponding diamines (I and II) with suitable difunctional acids, acid halides or dihalides under conventional polymer formng conditions.

The proportions of the reactants may be varied widely. They may be used in the ratio of 99.9 to 1 mole percent of diamine and 0.1 to 99 mole percent of the other reactant.

When the diamines are reacted with dibasic acids or their amide-forming derivatives, polyamides are obtained by conventional techniques. These polymers are useful for film or fiber applications where resistance to high temperature is desired. Suitable examples of dibasic acids or amide-forming derivatives thereof have their carboxylic groups separated by a hydrocarbyl diradical or alkylene group R of at least 3 carbons and preferably 4-14 carbons as derived from glutaric, adipic, pimelic, suberic, dodecanedioic, hexadecanedioic acids and their derivatives, especially the corresponding diacid halides which are more reactive. The latter form polymers readily by the interfacial polymerization technique with diacid chlorides or bromides. Also useful are dibasic acids or acid halides having aromatic residues in the chain such as of isophthalic or terephthalic acid. The resulting polyamides have the units as represented above separated by divalent radicals of the formula --CR-O wherein R is hydrocarbyl diradical or arylene radical of 6-14 carbons, preferably free from non-aromatic unsaturation as derived from terephthalic acid, isophthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 2-6-anthrancenedicarboxylic acid and 2,7 anthracenedicarboxylic acid. Thus R can be a polymethylene chain or an aromatic diradical.

Polyurethanes having the repeating units of the type described are also included. These have the diamino moiety separated by ester groups, i.e., in the divalent radical 0 O 4 -c-o-X-0cwherein X is alkylene or oxygen-interrupted alkylene radical of 2-14 chain atoms, such as wherein n is a number of generally 1-4. Other oxygencontaining radicals are propylene oxide and butylene oxide. The polymer-forming intermediates are easily obtained by reaction of the appropriate glycol with phosgene to give the chloroformates,

wherein C H or C H -O represent residues of ethylene glycol (11:2, m=1), polyethylene glycol (n=4, 6, 8, 10, m=l-4), propylene glycol and polypropylene glycol (e.g. 12:3, 6, 9, m=0, 1, 2), butylene glycol, hexamethylene glycol, etc.

Polyamines are a further type of polymer available from the novel diamines and are obtained by reaction of these diamines with a hydrocarbyl dichloride or dibromide wherein the chlorine or bromine are on aliphatic carbons. In this case the bridging means between two daimine residues is CH YCH wherein Y is alkylene of l to 14 carbon atoms or aryl of 6 to 14 carbons, e.g. as in methylene bromide, methylene chloride, 1,2-dibromoethane, 1,3 dibromopropane, 1,4-dichlorobutane, xylylene dibromide, 1,16-dibromohexadecane, and the like.

The polymers are formed from the above ingredients in conventional polymer-forming reactions and the formed polymers are inert, since there is no hydrogen on aminonitrogen and the amino-nitrogen is attached to carbon which has only one hydrogen. The polymers are useful for film and fiber applications where stability to the deleterious effects of heat and light are needed and can be used as wrapping films for many items of commerce.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A film forming polymer consisting essentially of a recurring structural unit of the group and - ----xr N wherein Q is 0 0 C-RC- and in which R is alkylene of 3 to 14 carbon atoms or arylene of 6 to 14 carbon atoms.

10 2. The polymer of claim 1 wherein the recurring struc- References Cited tural unit contains the saturated diamine moiety and the UNITED STATES PATENTS divalent organic radical R is alkylene of 4 carbon atoms.

3. The polymer of claim 1 wherein the recurring struc- 3301827 1/1967 Mamn 260*78 tural unit contains the saturated diamine moiety and the divalent organic radical R is arylene of six carbon atoms. 5 HAROLD D ANDERSON Primary Exammer 4. The polymer of claim 1 wherein the recurring struc- U S C1 X R tural unit contains the saturated diamine moiety and the divalent organic radical R is alkylene of 6 carbon atoms. 2602 B 5. A film of the polymer of claim 1. 10 6. A fiber of the polymer of claim 1.

. v I UNITED STATES PATENT OFFICE 1 CERTIFICATE OF CORREQ'HUN Patent No. 3, 35,9 Dated January 18, 197

I nventor(s) Alexander L. Johnson I Itv is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. l, the second member in the equation should be changed from 9 I c eh 9H v to COCl l v og;

Col; 5,. line 1 "E.. +.2.'.1 2 'l"" should be 001.5, line 13 00 a)" should be (00 K) Col. 7, lines 31 and 32, change "wherein D is a divalent organic radical selected from the to read wherein D is a divalent organic radical selected from the group consisting of Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORREQTTON Ptent No. 3,635,912 r Dared Jahuary 18; 1972 'Inventcr(s) Alexander L. Johnson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 8, line 9, correct the spelling of "anthracene" Col. 8,, line 42, correct the Spelling of "diamine Signed and sealed this 20th day of March 1973o (SEAL) Attest:

EDWARD M.FLE'I' CHER,JR. ROBERT GOT'ISCHALK Attestlng Officer v Commissioner of Patents 

